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United States Patent |
5,006,640
|
Drent
|
April 9, 1991
|
Polyketone with unsaturated terminal groups
Abstract
Contacting carbon monoxide and at least one .alpha.-olefin in a diluent
comprising at least 50% by volume of an aprotic polar compound in the
presence of a catalyst formed by contacting a palladium compound, the
anion of an acid having a pKa less than 4 and a bidentate phosphorus
ligand results in the production of novel polyketone polymers having
unsaturated end groups.
Inventors:
|
Drent; Eit (Amsterdam, NL)
|
Assignee:
|
Shell Oil Company (Houston, TX)
|
Appl. No.:
|
463706 |
Filed:
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January 11, 1990 |
Foreign Application Priority Data
Current U.S. Class: |
528/392 |
Intern'l Class: |
C08G 067/02 |
Field of Search: |
528/392
|
References Cited
U.S. Patent Documents
2495286 | Jan., 1950 | Brubaker | 260/63.
|
3694412 | Sep., 1972 | Nozaki | 260/63.
|
3984388 | Oct., 1976 | Shryne et al. | 260/63.
|
4843144 | Jun., 1989 | Van Broekhoven et al. | 528/392.
|
4880903 | Nov., 1989 | Van Broekhoven et al. | 528/392.
|
4904759 | Feb., 1990 | Drent | 528/392.
|
Foreign Patent Documents |
121965 | Oct., 1984 | EP.
| |
181014 | May., 1986 | EP.
| |
222454 | May., 1987 | EP.
| |
257663 | Mar., 1988 | EP.
| |
1081304 | Aug., 1967 | GB.
| |
Primary Examiner: Anderson; Harold D.
Parent Case Text
This is a division of application Ser. No. 271,130, filed Nov. 14, 1988,
now U.S. Pat. No. 4,921,938.
This invention relates to novel alternating polymers of carbon monoxide
with one or more olefinically unsaturated compounds.
Polymers of carbon monoxide and one or more ethylenically unsaturated
hydrocarbons are well known. Such polymers contain carbonyl groups in the
polymer backbone and are known as polyketones. The polymers are useful in
part because at least a portion of the carbonyl groups can be converted by
conventional chemical reactions into other functional groups, e.g.,
conversion into polyamines by reaction with ammonia and conversion into
polyols by catalytic hydrogenation. The polyketone polymers independently
have utility as will be described.
The carbon monoxide polymers produced by polymerization of carbon monoxide
and ethylenically unsaturated hydrocarbons such as ethylene are generally
high molecular weight linear alternating polymers having one unit of
carbon monoxide per unit of hydrocarbon. The polymers are typically
produced employing a catalyst comprising certain Group VIII metal
compounds, e.g., a palladium compound, an anion of an acid with a pKa less
than 4, and a bidentate phosphorus ligand represented by the formula
R.sup.1 R.sup.2 -P-R-P-R.sup.3 R.sup.4
wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 independently are organic
radicals, but preferably are similar, and R is a bivalent organic bridging
group having at least two carbon atoms in the bridge. When the
olefinically unsaturated hydrocarbon is ethylene, the polymers are
inexpensive and provide good mechanical properties of strength, stiffness
and impact resistance.
The preparation of the polymers by using the above-described catalyst
compositions may be carried out by contacting the monomers at an eIevated
temperature and pressure with a solution of the catalyst composition in a
protic polar diluent in which the polymers are insoluble or virtually
insoluble. During the polymerization, the polymers are obtained in the
form of a suspension in the diluent. After the desired degree of
polymerization is reached, the polymerization is generally terminated by
cooling and releasing the pressure. The polymers can be isolated from :he
suspension for instance by means of filtration or centrifugation. Lower
aliphatic alcohols, such as methanol have been found to be very suitable
protic polar diluents.
The type of diluent used has an effect on the terminal groups occurring in
the polymers. Thus, when carbon monoxide is polymerized with ethene in
methanol as the diluent and by using the above-mentioned catalyst
compositions, the resulting polymers will be substantially polymers which
can be represented by the formula CH.sub.3 --CH.sub.2 --CO--(C.sub.2
H.sub.4 --CO--).sub.n --CH.sub.2 --CH.sub.2 --CO --OCH.sub.3, i.e.
polymers whose molecules substantially bear an alkyl keto group at one end
and an alkyl ester group at the other end. With a view to the possible
uses of the polymers, it is desirable that either one of the terminal
groups in at least part of the polymer molecules should contain an
olefinically unsaturated double bond, so that the polymers can be suitably
used as a component in radical polymerization processes with olefinically
unsaturated monomers or with blefinically unsaturated polymers.
The Applicant has determined that conversion of the alkyl ester groups
which occur in the polymers as terminal groups into hydroxyl groups by
means of catalytic hydrogenation followed by catalytic dehydration is not
a suitable route to the introduction of an olefinically unsaturated double
bond into either one of the terminal groups of the polymer molecules.
Owing to various side reactions, for instance the deterioration of
carbonyl groups present in that polymer molecules, the polymer mixture
formed will be one in which much of the linear character of the polymers
is lost, while the introduction of an olefinically unsaturated double bond
into either of the two terminal groups of the polymer molecules remains
minimal.
SUMMARY OF THE INVENTION
The present invention includes certain novel polymers and a process of
producing the polymers. More particularly, the polymers of the invention
are polymers of carbon monoxide and at least one .alpha.-olefin with at
least a portion of the polymer molecules having a carbon-carbon double
bond in either of the two terminal groups. The polymers are linear
alternating polymers of carbon monoxide with the .alpha.-olefin, the
polymers having primarily units of the type --CO--(A)--wherein A is a
polymer component resulting from polymerization of the .alpha.-olefin.
Polymer component A preferably contains less than 10 carbon atoms and most
preferably ethylene is used to produce the polymer.
The polymers of the invention are produced by contacting the monomers in a
diluent consisting of more than 50 % by volume of one or more aprotic
polar compounds and in the presence of a catalyst comprising certain Group
VIII metal compounds, e.g., a palladium compound, an anion of an acid with
a pKa less than 4, and a bidentate phosphorus ligand represented by the
formula
R.sup.1, R.sup.2 --P-R-P-R.sup.3 R.sup.4
wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 independently are organic
radicals, but preferably are similar, and R is a bivalent organic bridging
group having at least two carbon atoms in the bridge. Preferred aprotic
polar compounds for providing the unsaturated terminal groups are dimethyl
sulfoxide and N-methyl-2-pyrrolidone. The polymerization of carbon
monoxide with ethylene in dimethyl sulphoxide as the diluent and using
catalyst compositions as mentioned hereinbefore will lead to polymers
which can be represented substantially by the following formula CH.sub.3
--CH.sub.2 --CO--(C.sub.2 H.sub.4 --CO--).sub.n --CH.sub.2 --CH.sub.2
--CO--CH .dbd.CH.sub.2, i.e. polymers whose molecules substantially bear
an alkyl keto group at one end and a vinyl keto group at the other end.
Preferably, more than 25% of the polymer molecules, and in particular more
than 40% of the polymer molecules of the polymers of the invention contain
an olefinically unsaturated double bond in either of the two terminal
groups.
Claims
What is claimed is:
1. A linear alternating polymer of carbon monoxide and at least one
.alpha.-olefin, the polymer comprising:
units of the formula --CO--(A)--wherein A is a mer unit from one or more
.alpha.-olefins; and
a least one polymer molecule that terminates with at least one group
containing a carbon-carbon double bond.
2. The polymer of claim 1 wherein A is a mer unit from an .alpha.-olefin
having less than 10 carbon atoms.
3. The polymer of claim 1 wherein A is a mer unit of ethylene.
4. The polymer of claim 1 wherein more than 40% of the polymer molecule
terminate with at least one group having a carbon-carbon double bond.
5. The polymer of claim 1 wherein more than 40% of the polymer molecules
terminate with at least one group having a carbon-carbon double bond.
6. The polymer of claim 1 wherein more than 25% of the polymer molecules
terminate with at least one --CH.dbd.CH.sub.2 group.
7. The polymer of claim 1 wherein more than 40% of the polymer molecules
terminate with at least one --CH.dbd.CH.sub.2 group.
Description
DESCRIPTION OF THE INVENTION
The polymers of the invention are linear alternating polymers of carbon
monoxide and at least one .alpha.-olefin with at least a portion of the
polymer molecules having a carbon-carbon double bond in either of the two
terminal groups. The polymers are linear alternating polymers of carbon
monoxide with the .alpha.-olefin, the polymers having primarily units of
the type --CO--(A)--wherein A is a polymer component resulting from
polymerization of the .alpha.-olefin.
The .alpha.-olefins employed to produce the units containing component A
have from 2 to 20, but preferably 2 to 10, carbon atoms inclusive. Useful
.alpha.-olefins are ethylene, propylene, and 1-butene. Polymerization is
most easily accomplished when a single o-olefin is employed and
particularly useful is ethylene.
The process of the invention comprises contacting carbon monoxide and the
.alpha.-olefin in the presence of a catalyst composition formed by
contacting a palladium compound, an anion of an acid having a pKa
(determined in aqueous solution at 18.degree. C.) less than 4, preferably
less than 2, and a bidentate phosphorus ligand represented by the formula
R.sup.1 R.sup.2 -P-R-P-R.sup.3 R.sup.4
wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 independently are organic
radicals which may or may not be aryl groups, but preferably are similar
aryl groups, and R is a bivalent organic bridging group having at least
two carbon atoms in the bridge.
The palladium compound employed in the catalyst compositions is a palladium
salt and preferably a palladium carboxylate such as palladium acetate. The
anion is an anion of an acid having a pKa less than about 4, such as
mineral acids including perchloric acid, sulfuric acid, phosphoric acid,
and nitrous acid, sulfonic acids including methanesulfonic acid,
trifluoromethanesulfonic acid, 2-hydroxypropane-2-sulionic acid, and
para-toluenesulfonic acid, and carboxylic acids including trichloroacetic
acid, dichloroacetic acid, trifluoroacetic acid, difluoroacetic acid,
tartaric acid, and Z,5-dihydroxybenzoic acid. Anions of acids having a pKa
less than 2 are prefered and in particular anions of sulfonic acids or
carboxylic acids, such as para-toluenesulfonic acid or trifluoroacetic
acid, respectively.
The anion is present in the catalyst composition in an amount from about
0.5 to about 200 equivalents per gram atom of palladium and preferably
from about 1 to about 100 equivalents per gram atom of palladium. The
anion is provided as the acid or as a salt of a non-noble transition metal
such as zirconium, vanadium, chromium, iron, nickel, copper or zinc. When
the anion is provided as the salt of a non-noble transition metal, a
copper salt is prefered. Optionally, the palladium compound and the anion
of the acid can be supplied as a single compound such as palladium
para-tosylate, having the formula Pd(CH.sub.3 CN).sub.2 (O.sub.3
S--C.sub.6 H.sub.4 --CH.sub.3).sub.2, which is prepared by reaction of
palladium chloride with the silver salt oi para-toluenesulfonic acid in
acetonitrile as the solvent or by reaction oi palladium acetate and
para-toluenesulfonic acid in acetonitrile as solvent.
In the phosphorus bidentate ligands having the formula R.sup.1 R.sup.2
-P-R-P-R.sup.3 R.sup.4 as described above, the preferred R group contains
3 atoms in the bridge with at least two of the atoms being carbon atoms.
Examples of suitable bridging groups R are the --CH.sub.2 --CH.sub.2
--CH.sub.2 --group, and the --CH.sub.2 --C(CH.sub.3).sub.2 --CH.sub.2
--group, the --CH.sub.2 --Si(CH.sub.3).sub.2 --CH.sub.2 --group, and the
--CH.sub.2 --C(R.sub.5)(R.sub.6)--CH.sub.2 -- group in which R.sub.5
represents a methyl group and R.sub.6 represents a diphenylphosphinomethyl
group. A very suitable phosphine ligand is
1,3-bis(diphen)lphosphino)propane. By preference, the phosphorus bidentate
ligands are used in a quantity from about 0.1 to about 3 mol per mol of
palladium compound, preferably from about(0.75 mol to about 3 mol per mol
of palladium compound.
The preparation of the polymers of the invention is carried out in a
diluent whIch comprises more than 50% by volume of one or more aprotic
polar compounds. Preferably, the diluent used comprises more than 75% by
volume of one or more aprotic polar compounds. Examples of suitable
aprotic polar diluent are dimethyl sulfoxide, N-methyl-Z-pyrrolidone,
N,N-dimethyl acetamide, and an acetonitrile. Preferred aprotic polar
diluents are dimethyl sulioxide and N-methyl-2-pyrrolidone. In addition to
one or more aprotic polar compounds, the diluent used may also include one
or more other compounds. Examples of such compounds are alcohols, such as
isopropanol, and ketones, such as acetone.
The catalyst composition useful in the process of the invention is employed
in quantities from about 1.times.10.sup.-7 mol to about 1.times.10.sup.-3
gram atom of palladium per mol of .alpha.-olefin are satisfactory with
quantities containing from about 1.times.10.sup.-6 to about
1.times.10.sup.-4 gram atom of palladium per mol of the o-olefin being
preferred. The molar ratio of the olefinically unsaturated compounds
relative to carbon monoxide is preferably 10:1 to 1:5 and most preferably
5:1 to 1:2.
The polymerization may be carried out either batchwise or continuous. In a
typical polymerization, conditions employed include reaction temperatures
from about 20.degree. C. to about 200.degree. C., preferably from about
30.degree. C. to about 150.degree. C. Typical reaction pressures vary from
about 1 to about 200 bar, preferably from about 20 to about 100 bar. The
carbon monoxide used in the polymerization may contain contaminants such
as hydrogen, carbon dioxide, and nitrogen. The mechanical form of the
reactor is not critical provided it maintains the desired polymerization
conditions of temperature and pressure. Subsequent to polymerization, the
terpolymer product is recovered by conventional means such as filtration
or decantation.
ILLUSTRATIVE EMBODIMENT I
A carbon monoxide/ethylene copolymer was prepared by charging to a
magnetically stirred autoclave of 250 ml capacity, a catalyst composition
solution comprising 50 ml of dimethyl sulfoxide, 0.1 mmol of palladium
acetate, 2 mmol of trifluoroacetic acid, and 0.15 mmol of
1,3-bis(diphenylphosphino)propane. After evacuation oi air present in the
autoclave, ethylene under pressure was added until a pressure of 20 bar
was reached. Then carbon monoxide was introduced under pressure until a
total pressure of 50 bar was reached. The contents of the autoclave were
heated and maintained at 80.degree. C. After 5 hours the polymerization
was terminated by cooling to room temperature and releasing pressure. The
polymer was filtered, washed with methanol and dried in under vacuum at
room temperature.
The polymerization rate was 160 grams of copolymer per gram of palladium
per hour. The copolymer contained unsaturated terminal groups at least at
one end in about 70 % of the polymer molecules on the average.
ILLUSTRATIVE EMBODIMENT II
The procedure of Illustrative Embodiment I was repeated except that (a) the
catalyst solution contained 50 ml of N-methyl-2-pyrrolidone and 5 ml of
isopropyl alcohol instead of dimethyl sulfoxide, and (b) the reaction time
was 3 hours.
The polymerization rate was 460 grams of copolymer per gram of palladium
per hour. The copolymer contained unsaturated terminal groups at least at
one end in about 90 % of the polymer molecules on the average.
ILLUSTRATIVE EMBODIMENT III
The procedure of Illustrative Embodiment I was repeated except that the
catalyst solution contained 50 ml of N-methyl-2-pyrrolidone instead of
dimethyl sulfoxide.
The polymerization rate was 360 grams of copolymer per gram of palladium
per hour. The copolymer contained unsaturated terminal groups at least at
one end in about 100 % of the polymer molecules on the average.
ILLUSTRATIVE EMBODIMENT IV
The procedure of Illustrative Embodiment I was repeated except that (a) the
catalyst solution contained 50 ml of N-methyl-2-pyrrolidone and 10 ml of
acetone instead of dimethyl sulfoxide, and lb) the reaction time was 1
hour.
The polymerization rate was 740 grams of copolymer per gram of palladium
per hour. The copolymer contained unsaturated terminal groups at least at
one end in about 90 % of the polymer molecules on the average.
ILLUSTRATIVE EMBODIMENT V
The procedure of Illustrative Embodiment I was repeated except that (a) the
catalyst solution contained 50 ml of N-methyl-2-pyrrolidone and 5 ml of
isopropyl alcohol instead of dimethyl sulfoxide, and 0.5 mmol of
para-toluenesulfonic acid instead of trifluoroacetic acid, and (b) the
reaction time was 2.5 hours.
The polymerization rate was 300 grams of copolymer per gram of palladium
per hour. The copolymer contained unsaturated terminal groups at least at
one end in about 50 % of the polymer molecules on the average.
With the aid of .sup.13 C-NMR analysis it was established that the
copolymers prepared according to Illustrative Embodiments I-V had a linear
structure and were made up of the units --CO--(C.sub.2 H.sub.4)--. It was
further established that the copolymers had the indicated amount of
unsaturated terminal groups.
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